CN114930593A - Solid electrolyte material and battery using the same - Google Patents

Solid electrolyte material and battery using the same Download PDF

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CN114930593A
CN114930593A CN202080092035.6A CN202080092035A CN114930593A CN 114930593 A CN114930593 A CN 114930593A CN 202080092035 A CN202080092035 A CN 202080092035A CN 114930593 A CN114930593 A CN 114930593A
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solid electrolyte
electrolyte material
battery
molar ratio
examples
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宫武和史
西尾勇祐
久保敬
浅野哲也
酒井章裕
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Panasonic Intellectual Property Management Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Conductive Materials (AREA)

Abstract

A solid electrolyte material is composed of Li, Y, X and O, wherein X is 1 selected from F, Cl, Br and I, and the molar ratio of O to Y is more than 0.01 and less than 0.52.

Description

Solid electrolyte material and battery using the same
Technical Field
The present disclosure relates to a solid electrolyte material and a battery using the same.
Background
Patent document 1 discloses an all-solid battery using a sulfide solid electrolyte. Patent document 2 discloses a lithium secondary battery made of Li 6-3z Y z X 6 (satisfy 0)<z<2, and X is Cl or Br).
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. 2011-129312
Patent document 2: international publication No. 2018/025582
Disclosure of Invention
Problems to be solved by the invention
An object of the present disclosure is to provide a solid electrolyte material having a low melting point and high ionic conductivity.
Means for solving the problems
The solid electrolyte material of the present disclosure is composed of Li, Y, X, and O, wherein X is 1 selected from F, Cl, Br, and I, and a molar ratio of O to Y is more than 0.01 and less than 0.52.
Effects of the invention
The present disclosure provides a solid electrolyte material having a low melting point and high ionic conductivity.
Drawings
Fig. 1 shows a cross-sectional view of a battery 1000 according to embodiment 2.
FIG. 2 is a diagram showing X-ray diffraction patterns of the solid electrolyte materials of examples 1 to 3 and comparative example 1.
Fig. 3 shows a schematic diagram of a press-forming die 300 used for evaluating the ion conductivity of a solid electrolyte material.
Fig. 4 is a Cole-Cole (Cole-Cole) diagram showing the impedance measurement result of the solid electrolyte material of example 1.
Fig. 5 is a graph showing the initial discharge characteristics of the battery of example 1.
FIG. 6 is a graph showing the results of thermal analysis in examples 1 to 3 and comparative example 1.
FIG. 7 is a graph showing X-ray diffraction patterns of the solid electrolyte materials of examples 4 to 6 and comparative examples 1 and 2.
Fig. 8 is a chart of a cole-cole plot showing the results of impedance measurement of the solid electrolyte material of example 4.
Fig. 9 is a graph showing the initial discharge characteristics of the battery of example 4.
FIG. 10 is a graph showing the results of thermal analysis in examples 4 to 6 and comparative examples 1 and 2.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described with reference to the drawings.
(embodiment 1)
The solid electrolyte material of embodiment 1 is composed of Li, Y, X, and O. Wherein, X is 1 selected from F, Cl, Br and I. The molar ratio of O relative to Y is greater than 0.01 and less than 0.52. The solid electrolyte material of embodiment 1 has a low melting point. Further, the solid electrolyte material of embodiment 1 has a high lithium ion conductivity. The low melting point is, for example, 504 ℃ or lower. That is, the solid electrolyte material of embodiment 1 may have a melting point of 504 ℃ or lower, for example. In the case where the solid electrolyte material is a heterogeneous material, the melting point of the solid electrolyte material means the highest temperature among the melting points of the solid electrolyte material. In addition, so-called high lithium ion conductivity such asIs 1 x 10 -5 S/cm or more. That is, the solid electrolyte material of embodiment 1 may have a melting point of 504 ℃ or lower and 1 × 10 -5 Ion conductivity of S/cm or more.
The solid electrolyte material according to embodiment 1 can be used to obtain an all-solid battery having excellent charge and discharge characteristics. The all-solid battery may be a primary battery, or may be a secondary battery.
The solid electrolyte material of embodiment 1 preferably does not contain sulfur. The sulfur-free solid electrolyte material is excellent in safety because hydrogen sulfide is not generated even when exposed to the atmosphere. The sulfide solid electrolyte disclosed in patent document 1 can generate hydrogen sulfide if exposed to the atmosphere.
The solid electrolyte material of embodiment 1 may be made of only Li, Y, X, and O.
In order to improve the ionic conductivity of the solid electrolyte material, the solid electrolyte material of embodiment 1 may further contain at least 1 selected from Mg, Ca, Zn, Sr, Ba, Al, Sc, Ga, Bi, La, Zr, Hf, Ta, and Nb.
The transition metal contained in the solid electrolyte material of the present embodiment may be Y alone, in addition to the elements contained as inevitable impurities.
X may also be Cl. Such a solid electrolyte material has a low melting point and high ionic conductivity.
Hereinafter, the following will describe example 1 and example 2 of the solid electrolyte material of embodiment 1. The 1 st example of the solid electrolyte material of embodiment 1 is described as a "1 st solid electrolyte material", and the 2 nd example of the solid electrolyte material of embodiment 1 is described as a "2 nd solid electrolyte material".
(the 1 st solid electrolyte material)
The X-ray diffraction pattern of the 1 st solid electrolyte material can be measured using Cu — ka radiation. In the obtained X-ray diffraction pattern, peaks may be present in the diffraction angle 2 θ ranges of 15.2 ° to 16.4 °, 16.7 ° to 18.6 °, 30.8 ° to 31.9 °, 33.2 ° to 34.3 °, 40.3 ° to 41.4 °, 48.2 ° to 49.3 °, and 53.0 ° to 54.2 °. Such a solid electrolyte material has a low melting point and high ionic conductivity.
In order to lower the melting point of the solid electrolyte material, the molar ratio of Li to Y may be 2.2 to 2.56, and the molar ratio of X to Y may be 3.5 to 5.9.
In order to further lower the melting point of the solid electrolyte material, the molar ratio of Li to Y may be 2.49 to 2.56, and the molar ratio of X to Y may be 3.91 to 5.29.
The molar ratio of O to Y may be, for example, 1.0 or less.
The upper limit and the lower limit of the molar ratio of O to Y may be defined by any combination of values selected from 0.01, 0.04, 0.23 and 0.50.
In order to lower the melting point of the solid electrolyte material, the molar ratio of O to Y may also be greater than 0.01 and 0.50 or less.
(No. 2 solid electrolyte Material)
The molar ratio a of O to Y in the surface region of the 2 nd solid electrolyte material may be larger than the molar ratio B of O to Y in the entire 2 nd solid electrolyte material. Such a solid electrolyte material has a low melting point and high ionic conductivity. As an example, the value of the molar ratio a may also be greater than 2 times the value of the molar ratio B.
The surface region of the 2 nd solid electrolyte material is a region of the 2 nd solid electrolyte material from the surface-inward direction to a depth of about 5 nm.
In order for the solid electrolyte material to have high ionic conductivity, the molar ratio a may also be 2.50 or less.
The X-ray diffraction pattern of the 2 nd solid electrolyte material can be measured using Cu — ka radiation. In the obtained X-ray diffraction pattern, peaks may be present in the diffraction angle 2 θ ranges of 15.2 ° to 16.3 °, 16.7 ° to 18.5 °, 30.8 ° to 31.9 °, 33.1 ° to 34.2 °, 40.3 ° to 41.4 °, 48.2 ° to 49.3 °, and 53.1 ° to 54.2 °. Such a solid electrolyte material has a low melting point and high ionic conductivity.
In order for the solid electrolyte material to have a low melting point and high ionic conductivity, the molar ratio of O to Y in the entire 2 nd solid electrolyte material may also be greater than 0.01 and 0.33 or less.
The shape of the solid electrolyte material of embodiment 1 is not limited. Examples of such shapes are needle-like, spherical or oval spherical. The solid electrolyte material of embodiment 1 may also be particles. The solid electrolyte material of embodiment 1 may also be formed to have a particle or plate shape.
When the solid electrolyte material of embodiment 1 is in the form of particles (for example, spheres), the solid electrolyte material of embodiment 1 may have a median particle diameter of 0.1 μm to 100 μm.
The median particle diameter may be 0.5 μm to 10 μm in order to improve the ionic conductivity of the solid electrolyte material of embodiment 1 and to disperse the solid electrolyte material and the active material of embodiment 1 well. The median diameter refers to a particle diameter in the case where the cumulative volume in the particle size distribution on a volume basis is equal to 50%. The volume-based particle size distribution can be measured by a laser diffraction measuring apparatus or an image analyzing apparatus.
In order to further favorably disperse the solid electrolyte material and the active material of embodiment 1, the solid electrolyte material of embodiment 1 may have a smaller median particle diameter than the active material.
< method for producing solid electrolyte Material >
The solid electrolyte material of embodiment 1 can be produced by the following method.
First, a plurality of halides are mixed as a raw material powder.
As an example, when a solid electrolyte material made of Li, Y, Cl and O is prepared, YCl is used 3 Mixing the raw material powder and LiCl raw material powder. The obtained mixed powder is fired in an inert gas atmosphere (for example, an argon atmosphere having a dew point of-60 ℃ or lower) in which the oxygen concentration and the water concentration are adjusted. The firing temperature may be, for example, 200 to 650 ℃. The resulting reaction product is in an atmosphere having a relatively high dew point (e.g., havingArgon atmosphere at a dew point of-30 ℃).
Then, the reaction product is burned at a temperature not lower than the melting point (for example, 550 ℃) in an inert gas atmosphere (for example, an argon atmosphere having a dew point of-60 ℃ or lower) in which the oxygen concentration and the water concentration are adjusted. By firing at a temperature equal to or higher than the melting point, O can be present in the entire material. Alternatively, as another example, the reaction product may be fired at a temperature of not more than the melting point (e.g., 400 ℃) in an inert gas atmosphere (e.g., an argon atmosphere having a dew point of not more than-60 ℃) in which the oxygen concentration and the water concentration are adjusted. By performing firing at a temperature lower than the melting point, the proportion of O in the surface region of the solid electrolyte material becomes large.
To counteract compositional variations that may arise in the synthesis process, the raw meal may also be mixed in a molar ratio that is adjusted beforehand. The amount of oxygen in the solid electrolyte material is determined by the selection of the raw material powder, the oxygen concentration in the atmosphere, the water concentration in the atmosphere, and the reaction time. In this manner, the solid electrolyte material according to embodiment 1 can be obtained.
The raw powder may be an oxide or a halide. For example, Y may be used as the raw material powder 2 O 3 、 NH 4 Cl and LiCl.
It is believed that: oxygen constituting the solid electrolyte material of embodiment 1 is taken in from the atmosphere having a relatively high dew point as described above.
(embodiment 2)
Hereinafter, embodiment 2 will be described. The matters described in embodiment 1 may be omitted.
The battery of embodiment 2 includes a positive electrode, a negative electrode, and an electrolyte layer. The electrolyte layer is disposed between the positive electrode and the negative electrode. At least 1 selected from the positive electrode, the electrolyte layer, and the negative electrode contains the solid electrolyte material according to embodiment 1. The battery of embodiment 2 contains the solid electrolyte material of embodiment 1, and therefore has excellent charge and discharge characteristics.
The solid electrolyte material having a low melting point is softer than the solid electrolyte material having a higher melting point. Therefore, the adhesion at the interface between the solid electrolyte materials or at the interface between the solid electrolyte material and another material (for example, an active material) is improved. As a result, the battery resistance is reduced, and thus the charge-discharge characteristics of the battery are improved. Furthermore, even if the solid electrolyte material is sintered with another material (for example, an active material), the occurrence of side reactions can be suppressed.
Fig. 1 shows a cross-sectional view of a battery 1000 according to embodiment 2.
The battery 1000 includes a positive electrode 201, an electrolyte layer 202, and a negative electrode 203.
The positive electrode 201 includes positive electrode active material particles 204 and solid electrolyte particles 100.
The electrolyte layer 202 is disposed between the positive electrode 201 and the negative electrode 203.
The electrolyte layer 202 contains an electrolyte material (e.g., a solid electrolyte material).
The negative electrode 203 contains negative electrode active material particles 205 and solid electrolyte particles 100.
The solid electrolyte particles 100 are particles made of the solid electrolyte material of embodiment 1 or particles containing the solid electrolyte material of embodiment 1 as a main component. Here, the "particles containing the solid electrolyte material of embodiment 1 as a main component" refers to particles containing the solid electrolyte material of embodiment 1 as the largest component.
The positive electrode 201 contains a material capable of inserting and extracting metal ions (for example, lithium ions). The material is, for example, a positive electrode active material (for example, positive electrode active material particles 204).
Examples of the positive electrode active material are lithium-containing transition metal oxides, transition metal fluorides, polyanionic materials, fluorinated polyanionic materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, or transition metal oxynitrides. An example of a lithium-containing transition metal oxide is LiNi 1-d-f Co d Al f O 2 (wherein, 0<d、0<f. And 0<(d+f)<1) Or LiCoO 2 。
In the positive electrode 201, the positive electrode active material particles 204 may have a median particle diameter of 0.1 μm or more in order to disperse the positive electrode active material particles 204 and the solid electrolyte particles 100 well. By this good dispersion, the charge and discharge characteristics of the battery 1000 are improved. The positive electrode active material particles 204 may have a median particle diameter of 100 μm or less in order to rapidly diffuse lithium in the positive electrode active material particles 204. Battery 1000 can operate at high output power due to rapid diffusion of lithium. As described above, the positive electrode active material particles 204 may have a median particle diameter of 0.1 μm to 100 μm.
In the positive electrode 201, the positive electrode active material particles 204 may have a larger median diameter than the solid electrolyte particles 100 in order to disperse the positive electrode active material particles 204 and the solid electrolyte particles 100 well.
In order to increase the energy density and output of the battery 1000, the ratio of the volume of the positive electrode active material particles 204 to the total of the volume of the positive electrode active material particles 204 and the volume of the solid electrolyte particles 100 in the positive electrode 201 may be 0.30 to 0.95.
In order to increase the energy density and output of battery 1000, positive electrode 201 may have a thickness of 10 μm to 500 μm.
The electrolyte layer 202 contains an electrolyte material. The electrolyte material may also include the solid electrolyte material of embodiment 1. The electrolyte layer 202 may be a solid electrolyte layer.
The electrolyte layer 202 may be formed of only the solid electrolyte material of embodiment 1. Alternatively, the electrolyte layer 202 may be composed of only a solid electrolyte material different from the solid electrolyte material of embodiment 1.
An example of a solid electrolyte material different from the solid electrolyte material of embodiment 1 is Li 2 MgX’ 4 、Li 2 FeX’ 4 、Li(Al，Ga，In)X’ 4 、Li 3 (Al，Ga，In)X’ 6 Or LiI. Wherein X' is at least 1 selected from F, Cl, Br and I.
The electrolyte layer 202 may contain not only the solid electrolyte material of embodiment 1 but also a solid electrolyte material different from the solid electrolyte material of embodiment 1. The solid electrolyte material of embodiment 1 and the solid electrolyte material different from the solid electrolyte material of embodiment 1 may also be uniformly dispersed. The layer formed of the solid electrolyte material of embodiment 1 and the layer formed of a solid electrolyte material different from the solid electrolyte material of embodiment 1 may be laminated along the lamination direction of the battery 1000.
In order to suppress short circuit between the positive electrode 201 and the negative electrode 203 and to improve the output of the battery 1000, the electrolyte layer 202 may have a thickness of 1 μm to 100 μm.
The negative electrode 203 contains a material capable of inserting and extracting metal ions (for example, lithium ions). The material is, for example, a negative electrode active material (for example, negative electrode active material particles 205).
Examples of the negative electrode active material are a metal material, a carbon material, an oxide, a nitride, a tin compound, or a silicon compound. The metal material may be a simple metal or an alloy. Examples of the metallic material are lithium metal or lithium alloy. Examples of carbon materials are natural graphite, coke, carbon in the graphitizing medium, carbon fibers, spherical carbon, artificial graphite or amorphous carbon. From the viewpoint of capacity density, preferable examples of the negative electrode active material are silicon (i.e., Si), tin (i.e., Sn), a silicon compound, or a tin compound.
In the negative electrode 203, the negative electrode active material particles 205 may have a median particle diameter of 0.1 μm or more in order to disperse the negative electrode active material particles 205 and the solid electrolyte particles 100 well. By this good dispersion, the charge-discharge characteristics of the battery are improved. In order to rapidly diffuse lithium in the negative electrode active material particles 205, the negative electrode active material particles 205 may have a median particle diameter of 100 μm or less. The battery can operate at high output power due to rapid diffusion of lithium. As described above, the negative electrode active material particles 205 may have a median particle diameter of 0.1 μm to 100 μm.
In the negative electrode 203, the negative electrode active material particles 205 may have a larger median diameter than the solid electrolyte particles 100 in order to disperse the negative electrode active material particles 205 and the solid electrolyte particles 100 well.
In order to increase the energy density and output of the battery 1000, the ratio of the volume of the negative electrode active material particles 205 to the total of the volume of the negative electrode active material particles 205 and the volume of the solid electrolyte particles 100 in the negative electrode 203 may be 0.30 to 0.95.
In order to increase the energy density and output of the battery 1000, the negative electrode 203 may have a thickness of 10 μm to 500 μm.
In order to improve the ionic conductivity, chemical stability, and electrochemical stability, at least 1 selected from the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a solid electrolyte material different from the solid electrolyte material of embodiment 1.
Examples of the solid electrolyte material are a halide solid electrolyte, a sulfide solid electrolyte, an oxide solid electrolyte, or an organic polymer solid electrolyte.
An example of a halide solid electrolyte is Li 2 MgX’ 4 、Li 2 FeX’ 4 、Li(Al，Ga，In)X’ 4 、 Li 3 (Al，Ga，In)X’ 6 Or LiI. Wherein X' is at least 1 selected from F, Cl, Br and I.
An example of a sulfide solid electrolyte is Li 2 S-P 2 S 5 、Li 2 S-SiS 2 、Li 2 S-B 2 S 3 、Li 2 S-GeS 2 、 Li 3.25 Ge 0.25 P 0.75 S 4 Or Li 10 GeP 2 S 12 。
Examples of oxide solid electrolytes are:
(i)LiTi 2 (PO 4 ) 3 or an element-substituted body thereof, and a solid electrolyte of NASICON type,
(ii)(LaLi)TiO 3 Such a perovskite type solid electrolyte,
(iii)Li 14 ZnGe 4 O 16 、Li 4 SiO 4 、LiGeO 4 Or an element-substituted form thereof,
(iv)Li 7 La 3 Zr 2 O 12 Or a garnet-type solid electrolyte such as a substitution product of the element, or
(v)Li 3 PO 4 Or an N-substitution thereof.
Examples of the organic polymer solid electrolyte include a polymer compound and a lithium salt compound. The polymer compound may have an ethylene oxide structure. Since the polymer compound having an ethylene oxide structure can contain a large amount of lithium salt, the ionic conductivity can be further improved.
An example of the lithium salt is LiPF 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiSO 3 CF 3 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 C 2 F 5 ) 2 、LiN(SO 2 CF 3 )(SO 2 C 4 F 9 ) Or LiC (SO) 2 CF 3 ) 3 . The 1 lithium salt selected from them may also be used alone. Alternatively, a mixture of 2 or more lithium salts selected from them may also be used.
At least 1 selected from the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a nonaqueous electrolytic solution, a gel electrolyte, or an ionic liquid for the purpose of facilitating the transfer of lithium ions and improving the output characteristics of the battery 1000.
The nonaqueous electrolyte solution contains a nonaqueous solvent and a lithium salt dissolved in the nonaqueous solvent.
Examples of the nonaqueous solvent are a cyclic carbonate solvent, a chain carbonate solvent, a cyclic ether solvent, a chain ether solvent, a cyclic ester solvent, a chain ester solvent, or a fluorine solvent. Examples of the cyclic carbonate solvent are ethylene carbonate, propylene carbonate or butylene carbonate. Examples of the chain carbonate solvent are dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate. Examples of cyclic ether solvents are tetrahydrofuran, 1, 4-dioxane or 1, 3-dioxolane. Examples of the chain ether solvent are 1, 2-dimethoxyethane or 1, 2-diethoxyethane. An example of a cyclic ester solvent is gamma-butyrolactone. An example of a chain ester solvent is methyl acetate. Examples of fluorosolvents are fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, ethylmethyl fluorocarbonate or dimethylene fluorocarbonate.
The 1 kind of nonaqueous solvent selected from them may be used alone. Alternatively, a mixture of 2 or more kinds of nonaqueous solvents selected from them may be used.
An example of the lithium salt is LiPF 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiSO 3 CF 3 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 C 2 F 5 ) 2 、LiN(SO 2 CF 3 )(SO 2 C 4 F 9 ) Or LiC (SO) 2 CF 3 ) 3 . The 1 lithium salt selected from them may also be used alone. Alternatively, a mixture of 2 or more lithium salts selected from them may also be used.
The concentration of the lithium salt is, for example, in the range of 0.5 mol/l to 2 mol/l.
As the gel electrolyte, a polymer material impregnated with a nonaqueous electrolytic solution can be used. Examples of polymeric materials are polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate or polymers having ethylene oxide bonds.
Examples of cations contained in the ionic liquid are:
(i) aliphatic chain quaternary salts such as tetraalkylammonium and tetraalkylphosphonium,
(ii) Aliphatic cyclic ammonium such as pyrrolidinium, morpholinium, imidazolinium, tetrahydropyrimidinium, piperazinium or piperidinium, or
(iii) Nitrogen-containing heterocyclic aromatic cations such as pyridinium and imidazolium.
An example of an anion contained in the ionic liquid is PF 6 - 、BF 4 - 、SbF 6 - 、AsF 6 - 、SO 3 CF 3 - 、 N(SO 2 CF 3 ) 2 - 、N(SO 2 C 2 F 5 ) 2 - 、N(SO 2 CF 3 )(SO 2 C 4 F 9 ) - Or C (SO) 2 CF 3 ) - 3。
The ionic liquid may also contain a lithium salt.
At least 1 selected from the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder for the purpose of improving adhesion between particles.
Examples of binders are polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resins, polyamides, polyimides, polyamideimides, polyacrylonitrile, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polyhexamethylene acrylate, polymethacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polyhexamethylene methacrylate, polyvinyl acetate, polyvinyl pyrrolidone, polyethers, polyether sulfones, hexafluoropropylene, styrene butadiene rubber or carboxymethylcellulose.
The copolymer may also be used as a binder. Examples of such binders are copolymers of 2 or more materials selected from tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene. A mixture of 2 or more selected from them may also be used as the binder.
In order to improve electron conductivity, at least 1 selected from the positive electrode 201 and the negative electrode 203 may contain a conductive auxiliary agent.
Examples of the conductive assistant are:
(i) graphite such as natural graphite or artificial graphite,
(ii) Carbon blacks such as acetylene black and ketjen black,
(iii) Conductive fibers such as carbon fibers or metal fibers,
(iv) Carbon fluoride,
(v) Metal powders such as aluminum,
(vi) Conductive whiskers such as zinc oxide or potassium titanate,
(vii) A conductive metal oxide such as titanium oxide, or
(viii) And conductive polymer compounds such as polyaniline, polypyrrole, and polythiophene.
The conductive assistant (i) or (ii) may be used for cost reduction.
Examples of the shape of the battery according to embodiment 2 include a coin shape, a cylindrical shape, a rectangular shape, a sheet shape, a button shape, a flat shape, and a laminated shape.
The battery according to embodiment 2 can be manufactured, for example, by: a material for forming a positive electrode, a material for forming an electrolyte layer, and a material for forming a negative electrode were prepared, and a laminate in which a positive electrode, an electrolyte layer, and a negative electrode were arranged in this order was produced by a known method.
Examples
Hereinafter, the present disclosure will be described in more detail with reference to examples.
(example 1)
[ production of solid electrolyte Material ]
Subjecting the resultant powder to YCl in an argon atmosphere having a dew point of-60 ℃ or lower and an oxygen concentration of 0.0001 vol% or lower (hereinafter referred to as "dry argon atmosphere") to obtain a raw powder 3 : the LiCl molar ratio is 1: mode 3 preparation of YCl 3 And LiCl. These raw material powders were pulverized and mixed in a mortar. The resulting mixture was fired at 550 ℃ for 1 hour in an alumina crucible, and then pulverized in a mortar. The resulting reaction product was allowed to stand for about 10 minutes in an argon atmosphere having a dew point of-30 ℃ and an oxygen concentration of 20.9 vol%. Further, the mixture was calcined at 550 ℃ for 1 hour in a dry argon atmosphere, and then pulverized in a mortar. In this manner, a solid electrolyte material of example 1 was obtained.
[ composition analysis of solid electrolyte Material ]
The contents of Li and Y per unit weight of the solid electrolyte material of example 1 were measured by high-frequency inductively coupled plasma emission spectrometry using a high-frequency inductively coupled plasma emission spectrometer (manufactured by Thermo Fisher Scientific, iCAP 7400). The Cl content of the solid electrolyte material of example 1 was measured by ion chromatography using an ion chromatography apparatus (available from Dionex, ICS-2000). Based on the contents of Li, Y and Cl obtained from these measurement results, Li: y: cl molar ratio. As a result, the solid electrolyte material of example 1 had a mass ratio of 2.56: 1.00: 5.29 Li: y: cl molar ratio.
The mass ratio of O to the entire solid electrolyte material in example 1 was measured by a non-dispersive infrared absorption method using an oxynitric hydrogen analyzer (EMGA-930, manufactured by horiba ltd.). As a result, the mass ratio of O was 0.22%. Based on this, Y: and (3) the molar ratio of O. As a result, the solid electrolyte material of example 1 had a mass ratio of 1.00: 0.04Y: and (3) the molar ratio of O.
In the composition analysis, an element in a molar ratio of 0.001% or less with respect to Y is regarded as an impurity.
[ measurement of melting Point ]
For the measurement of the melting point, a thermal analyzer (Q1000, manufactured by t.a. instruments) was used. The solid electrolyte material of example 1 (about 5mg) was weighed in a nitrogen atmosphere, and heated from 300 ℃ to 530 ℃ at a temperature increase rate of 10K/min. An endothermic peak at this time was observed. Based on the obtained data, a two-dimensional graph was prepared with the horizontal axis as temperature and the vertical axis as heat generation amount. Points 2 on the graph where the solid electrolyte material neither generates heat nor absorbs heat are connected by a straight line, and this is taken as a baseline. Next, the intersection of the tangent line at the inflection point of the endothermic peak and the base line was set as the melting point. As a result, the melting point of the solid electrolyte material of example 1 was 500.6 ℃. Fig. 6 is a graph showing the results of thermal analysis of the solid electrolyte material of example 1.
[ X-ray diffraction ]
An X-ray diffraction apparatus (RIGAKU, MiniFlex600) was used for analysis of the crystal structure of the solid electrolyte material. The X-ray diffraction pattern of the solid electrolyte material of example 1 was measured in a dry environment having a dew point of-45 ℃ or lower. As the X-ray source, Cu-Ka rays (wavelength: X-ray)
Figure BDA0003729887630000121
And
Figure BDA0003729887630000122
)。
as a result of X-ray diffraction measurement, peaks were present at 15.83 °, 18.03 °, 31.37 °, 33.72 °, 40.85 °, 48.74 °, and 53.58 °. Fig. 2 is a diagram showing an X-ray diffraction pattern of the solid electrolyte material of example 1.
[ evaluation of ion conductivity ]
Fig. 3 shows a schematic diagram of a press-forming die 300 used for evaluating the ionic conductivity of a solid electrolyte material.
The press-forming die 300 includes a punch upper portion 301, a frame shape 302, and a punch lower portion 303. Frame 302 is formed of insulating polycarbonate. The punch upper part 301 and the punch lower part 303 are both formed of electrically conductive stainless steel.
The ion conductivity of the solid electrolyte material of example 1 was measured by the following method using a press-forming die 300 shown in fig. 3.
The powder 101 of the solid electrolyte material of example 1 was filled inside the press-forming die 300 in a dry argon atmosphere. Inside the press molding die 300, a pressure of 400MPa was applied to the solid electrolyte material of example 1 using the punch upper part 301 and the punch lower part 303.
The upper punch portion 301 and the lower punch portion 303 are connected to a potentiostat (Princeton Applied Research, Versa STAT4) in a pressurized state. The punch upper portion 301 is connected to the working electrode and the potential measuring terminal. The punch lower portion 303 is connected to the counter electrode and the reference electrode. The impedance of the solid electrolyte material of example 1 was measured by electrochemical impedance measurement at room temperature.
Fig. 4 is a cole-cole plot showing the results of impedance measurement of the solid electrolyte material of example 1.
In fig. 4, the real value of the impedance at the measurement point where the absolute value of the phase of the complex impedance is smallest is regarded as the resistance value of the solid electrolyte material for ion conduction. For the real value, refer to arrow R shown in FIG. 4 SE . Using this resistance value, the ion conductivity was calculated based on the following equation (1).
σ＝(R SE ×S/t) -1 (1)
Where σ is the ionic conductivity. S is the contact area of the solid electrolyte material with the punch upper portion 303 (equal to the cross-sectional area of the hollow portion of the frame 301 in fig. 3). R SE Is the resistance value of the solid electrolyte material in the impedance measurement. t is the thickness of the solid electrolyte material to which pressure is applied (in fig. 3, equal to the thickness of the layer formed of the powder 101 of the solid electrolyte material).
The ionic conductivity of the solid electrolyte material of example 1 measured at 25 ℃ was 2.4X 10 -4 S/cm。
[ production of Battery ]
In a dry argon atmosphere, the ratio as 70: preparation of solid electrolyte Material and LiCoO as an active Material in example 1 to prepare a volume ratio of 30 2 . These materials were mixed in an agate mortar. In this manner, a mixture was obtained.
The solid electrolyte material (100mg) of example 1, the mixture (10.0mg) and the aluminum powder (14.7mg) were stacked in this order in an insulating cylinder having an inner diameter of 9.5 mm. A pressure of 300MPa was applied to the laminate to form the 1 st electrode and the solid electrolyte layer. The solid electrolyte layer had a thickness of 500 μm.
Next, a metal In foil was laminated on the solid electrolyte layer. The solid electrolyte layer is sandwiched between the metal In foil and the 1 st electrode. The metallic In foil has a thickness of 200 μm. Subsequently, a pressure of 80MPa was applied to the metal In foil to form a 2 nd electrode.
Current collectors made of stainless steel were attached to the 1 st and 2 nd electrodes, and then current collecting leads were attached to the current collectors. Finally, the inside of the insulating cylinder is sealed by using an insulating ferrule while blocking the inside of the insulating cylinder from the outside air atmosphere. In this manner, a battery of example 1 was obtained.
[ Charge/discharge test ]
Fig. 5 is a graph showing the initial discharge characteristics of the battery of example 1. The results shown in fig. 5 were measured by the following method.
The battery of example 1 was configuredIn a thermostatic bath at 25 ℃. At 86 μ A/cm 2 The battery of example 1 was charged until a voltage of 3.7V was reached. This current density corresponds to a 0.05C magnification. Then, the same procedure was carried out at 86. mu.A/cm 2 The battery of example 1 was discharged until a voltage of 1.9V was reached.
As a result of the charge and discharge test, the battery of example 1 had an initial discharge capacity of 536 μ Ah.
(examples 2 and 3)
A solid electrolyte material of example 2 was obtained in the same manner as in example 1, except that the time for leaving the reaction product in an atmosphere having a dew point of-30 ℃ was set to 30 minutes instead of about 10 minutes.
A solid electrolyte material of example 3 was obtained in the same manner as in example 1, except that the time for leaving the reaction product in an atmosphere having a dew point of-30 ℃ was set to 9 hours instead of about 10 minutes.
The element ratio (molar ratio), melting point, oxygen amount, X-ray diffraction, and ion conductivity of the solid electrolyte materials of examples 2 and 3 were measured in the same manner as in example 1. The measurement results are shown in tables 1 and 2. Fig. 2 is a diagram showing X-ray diffraction patterns of the solid electrolyte materials of examples 2 and 3. Fig. 6 is a graph showing the results of thermal analysis of the solid electrolyte materials of examples 2 and 3.
Batteries of examples 2 and 3 were obtained in the same manner as in example 1, using the solid electrolyte materials of examples 2 and 3.
Charge and discharge tests were carried out using the batteries of examples 2 and 3 in the same manner as in example 1. The batteries of examples 2 and 3 were charged and discharged as well as the battery of example 1.
Comparative example 1
In a dry argon atmosphere, as a raw material powder, according to YCl 3 : the LiCl molar ratio is 1: mode 3 preparation of YCl 3 And LiCl. These raw material powders were pulverized and mixed in a mortar. The resulting mixture was fired at 550 ℃ for 1 hour in an alumina crucible, and then pulverized in a mortar. Like thisIn this manner, a solid electrolyte material of comparative example 1 was obtained.
The solid electrolyte material of comparative example 1 was measured for the element ratio (molar ratio), melting point, oxygen amount, X-ray diffraction, and ion conductivity in the same manner as in example 1. The measurement results are shown in tables 1 and 2. Fig. 2 is a diagram showing an X-ray diffraction pattern of the solid electrolyte material of comparative example 1. Fig. 6 is a graph showing the results of thermal analysis of the solid electrolyte material of comparative example 1.
[ Table 1]
Figure BDA0003729887630000151
[ Table 2]
Figure BDA0003729887630000152
(examination)
As is apparent from table 1, the solid electrolyte materials of examples 1 to 3 had lower melting points than the solid electrolyte material of comparative example 1. Further, the solid electrolyte materials of examples 1 to 3 had a thickness of 1X 10 in the vicinity of room temperature -5 High ionic conductivity of S/cm or more.
The batteries of examples 1-3 were charged and discharged at 25 ℃.
The solid electrolyte materials of examples 1 to 3 did not generate hydrogen sulfide because they did not contain sulfur.
(example 4)
[ production of solid electrolyte Material ]
In a dry argon atmosphere, as a raw material powder, according to YCl 3 : the LiCl molar ratio is 1: preparation of YCl in 3 mode 3 And LiCl. These raw material powders were pulverized and mixed in a mortar. The resulting mixture was fired at 550 ℃ for 1 hour in an alumina crucible, and then pulverized in a mortar. The resulting reaction product was allowed to stand for about 10 minutes in an argon atmosphere having a dew point of-30 ℃ and an oxygen concentration of 20.9 vol%. Further, firing is carried out at 400 ℃ in a dry argon atmosphereAfter 1 hour, pulverize in a mortar. In this manner, a solid electrolyte material of example 4 was obtained.
[ composition analysis of solid electrolyte Material ]
In the same manner as in example 1, the contents of Li, Y, and Cl in the entire solid electrolyte material of example 4 were measured, and Li: y: cl molar ratio. As a result, the solid electrolyte material of example 4 had a composition of 2.56: 1.00: 5.16 Li: y: cl molar ratio.
In the same manner as in example 1, the mass ratio of O to the entire solid electrolyte material in example 4 was measured. As a result, the mass ratio of O was 0.29%. Based on this, Y: and (3) the molar ratio of O. As a result, the solid electrolyte material of example 4 had a mass ratio of 1.00: 0.06Y: and (3) the molar ratio of O.
The molar ratio of O to Y in the surface region of the solid electrolyte material in example 4 was measured by X-ray photoelectron spectroscopy using a scanning X-ray photoelectron spectroscopic analyzer (ULVAC-PHI, manufactured by INCORPORATED, PHI Quantera SXM). The X-ray source uses Al-K α radiation. As a result, the solid electrolyte material of example 4 had a surface area of 1.00: 0.15Y: and (3) the molar ratio of O. The surface region in the present disclosure refers to a region measured by performing the above-described operation. The thickness of the surface region of the solid electrolyte material of example 4 was about 5nm in the inward direction from the surface of the solid electrolyte material.
In the composition analysis, an element in a molar ratio of 0.001% or less with respect to Y is regarded as an impurity.
[ measurement of melting Point ]
The melting point of the solid electrolyte material of example 4 was measured in the same manner as in example 1. As a result, the melting point of the solid electrolyte material of example 4 was 498.8 ℃. Fig. 10 is a graph showing the results of thermal analysis of the solid electrolyte material of example 4.
[ X-ray diffraction ]
The X-ray diffraction pattern of the solid electrolyte material of example 4 was measured in the same manner as in example 1.
As a result of X-ray diffraction measurement, peaks were present at 15.79 °, 17.99 °, 31.33 °, 33.67 °, 40.84 °, 48.74 °, and 53.56 °. Fig. 7 is a diagram showing an X-ray diffraction pattern of the solid electrolyte material of example 4.
[ Charge/discharge test ]
A battery of example 4 was obtained in the same manner as in example 1, using the solid electrolyte material of example 4.
Fig. 9 is a graph showing the initial discharge characteristics of the battery of example 4. The results shown in fig. 9 were measured by the following method.
The cell of example 4 was placed in a thermostatic bath at 25 ℃. At 83 μ A/cm 2 The battery of example 7 was charged until a voltage of 3.7V was reached. This current density corresponds to a 0.05C-rate. Then, the same rate was applied at 83. mu.A/cm 2 The battery of example 4 was discharged until a voltage of 1.9V was reached.
As a result of the charge and discharge test, the battery of example 4 had an initial discharge capacity of 642 μ Ah.
(examples 5 and 6)
A solid electrolyte material of example 5 was obtained in the same manner as in example 4, except that the time for which the reaction product was left to stand in the atmosphere having a dew point of-30 ℃ was set to 30 minutes instead of about 10 minutes.
A solid electrolyte material of example 6 was obtained in the same manner as in example 4, except that the time for leaving the reaction product in an atmosphere having a dew point of-30 ℃ was set to 2 hours instead of about 10 minutes.
The element ratio (molar ratio), melting point, oxygen amount, X-ray diffraction, and ion conductivity of the solid electrolyte materials of examples 5 and 6 were measured in the same manner as in example 4. The measurement results are shown in tables 3 and 4. Fig. 7 is a diagram showing X-ray diffraction patterns of the solid electrolyte materials of examples 5 and 6. Fig. 10 is a graph showing the results of thermal analysis of the solid electrolyte materials of examples 5 and 6.
Batteries of examples 5 and 6 were obtained in the same manner as in example 1, using the solid electrolyte materials of examples 5 and 6.
Charge and discharge tests were carried out in the same manner as in example 4 using the batteries of examples 5 and 6. The batteries of examples 5 and 6 were charged and discharged as well as the battery of example 4.
Comparative example 2
A solid electrolyte material of comparative example 2 was obtained in the same manner as in example 7, except that the time for leaving the reaction product in an atmosphere having a dew point of-30 ℃ was set to 9 hours instead of about 10 minutes.
The solid electrolyte materials of comparative examples 1 and 2 were measured for element ratio (molar ratio), melting point, oxygen amount, X-ray diffraction, and ion conductivity in the same manner as in example 7. The measurement results are shown in tables 3 and 4. Fig. 7 is a diagram showing X-ray diffraction patterns of the solid electrolyte materials of comparative examples 1 and 2. Fig. 10 is a graph showing the results of thermal analysis of the solid electrolyte materials of comparative examples 1 and 2.
A battery of comparative example 2 was obtained in the same manner as in example 4 using the solid electrolyte material of comparative example 2.
A charge/discharge test was carried out using the battery of comparative example 2 in the same manner as in example 4, but the initial discharge capacity was 1mAh or less. The battery of comparative example 2 was neither charged nor discharged.
[ Table 3]
Figure BDA0003729887630000181
[ Table 4]
Figure BDA0003729887630000182
(examination)
As is apparent from table 3, the solid electrolyte materials of examples 4 to 6 had lower melting points than the solid electrolyte material of comparative example 1. Further, the solid electrolyte materials of examples 4 to 6 had a thickness of 1X 10 in the vicinity of room temperature -5 High ionic conductivity of S/cm or more. On the other hand, of comparative example 2The solid electrolyte material has a thickness of less than 1 x 10 -5 Ion conductivity of S/cm.
As is apparent from table 3, if the molar ratio of O to Y in the entirety of the solid electrolyte material is more than 0.01 and 0.33 or less, the solid electrolyte material has a low melting point and high ionic conductivity.
The batteries of examples 4-6 were charged and discharged at 25 ℃.
The solid electrolyte materials of examples 4 to 6 did not generate hydrogen sulfide because they did not contain sulfur.
As described above, the solid electrolyte material of the present disclosure is suitable for providing a battery having a low melting point and a high lithium ion conductivity and capable of being charged and discharged well.
Industrial applicability
The solid electrolyte material of the present disclosure is utilized in, for example, an all-solid lithium ion secondary battery.
Description of the symbols
100 solid electrolyte plasmid
101 powder of solid electrolyte material
201 positive electrode
202 electrolyte layer
203 negative electrode
204 positive electrode active material particle
205 negative electrode active material particle
300 press forming die
301 punch top
302 frame type
303 lower part of punch
1000 cells.

Claims (10)

1. A solid electrolyte material composed of Li, Y, X and O,
wherein X is 1 selected from F, Cl, Br and I, and
the molar ratio of O relative to Y is greater than 0.01 and less than 0.52.
2. The solid electrolyte material according to claim 1, wherein X is Cl.
3. The solid electrolyte material according to claim 1 or 2, further comprising at least 1 selected from Mg, Ca, Zn, Sr, Ba, Al, Sc, Ga, Bi, La, Zr, Hf, Ta, and Nb.
4. The solid electrolyte material according to any one of claims 1 to 3, wherein in an X-ray diffraction pattern obtained by X-ray diffraction measurement using Cu-Ka, peaks exist in the ranges of diffraction angles 2 θ of 15.2 ° to 16.4 °, 16.7 ° to 18.6 °, 30.8 ° to 31.9 °, 33.2 ° to 34.3 °, 40.3 ° to 41.4 °, 48.2 ° to 49.3 °, and 53.0 ° to 54.2 °.
5. The solid electrolyte material according to any one of claims 1 to 4, wherein a molar ratio of Li to Y is 2.2 to 2.56, and
the molar ratio of X to Y is 3.5 to 5.9.
6. The solid electrolyte material according to any one of claims 1 to 5, wherein a molar ratio of O to Y is more than 0.01 and 0.50 or less.
7. The solid electrolyte material according to any one of claims 1 to 3, wherein a molar ratio of O to Y in a surface region of the solid electrolyte material is larger than a molar ratio of O to Y in the entirety of the solid electrolyte material.
8. The solid electrolyte material according to any one of claims 1 to 3 and 7, wherein in an X-ray diffraction pattern obtained by X-ray diffraction measurement using Cu-Ka, peaks exist in the ranges of diffraction angles 2 θ of 15.2 ° to 16.3 °, 16.7 ° to 18.5 °, 30.8 ° to 31.9 °, 33.1 ° to 34.2 °, 40.3 ° to 41.4 °, 48.2 ° to 49.3 °, and 53.1 ° to 54.2 °.
9. The solid electrolyte material according to any one of claims 1 to 3, 7 and 8, wherein a molar ratio of O to Y in the entire solid electrolyte material is greater than 0.01 and 0.33 or less.
10. A battery is provided with:
a positive electrode;
a negative electrode; and
an electrolyte layer disposed between the positive electrode and the negative electrode,
wherein at least 1 selected from the group consisting of the positive electrode, the negative electrode and the electrolyte layer contains the solid electrolyte material according to any one of claims 1 to 9.
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